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Title: High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries

Abstract

Using fast time-resolved in situ X-ray diffraction, charge-rate dependent phase transition processes of layer structured cathode material LiNi 1/3Mn 1/3Co 1/3O 2 for lithium-ion batteries are studied. During first charge, intermediate phases emerge at high rates of 10C, 30C, and 60C, but not at low rates of 0.1C and 1C. These intermediate phases can be continuously observed during relaxation after the charging current is switched off. After half-way charging at high rate, sample studied by scanning transmission electron microscopy shows Li-rich and Li-poor phases' coexistence with tetrahedral occupation of Li in Li-poor phase. Also, the high rate induced overpotential is thought to be the driving force for the formation of this intermediate Li-poor phase. The in situ quick X-ray absorption results show that the oxidation of Ni accelerates with increasing charging rate and the Ni 4+ state can be reached at the end of charge with 30C rate. Finally, these results give new insights in the understanding of the layered cathodes during high-rate charging.

Authors:
 [1];  [2];  [3];  [4];  [4];  [5];  [3];  [3];  [3];  [6];  [6];  [2];  [3]
  1. Fudan Univ., Shanghai (China). Department of Materials Science; Brookhaven National Lab. (BNL), Upton, NY (United States). Department of Chemistry
  2. Fudan Univ., Shanghai (China). Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Department of Chemistry & Laser Chemistry Institute
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Department of Chemistry
  4. Chinese Academy of Sciences (CAS), Beijing (China). Laboratory for Advanced Materials & Electron Microscopy, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics
  5. Dongguk University-Seoul, Seoul (Republic of Korea). Department of Energy and Materials Engineering
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1336072
Report Number(s):
BNL-112452-2016-JA
Journal ID: ISSN 1614-6832; R&D Project: MA453MAEA; VT1201000
Grant/Contract Number:
SC0012704; AC02-98CH10886; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 21; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; National Synchrotron Light Source II

Citation Formats

Zhou, Yong-Ning, Yue, Ji-Li, Hu, Enyuan, Li, Hong, Gu, Lin, Nam, Kyung-Wan, Bak, Seong-Min, Yu, Xiqian, Liu, Jue, Bai, Jianming, Dooryhee, Eric, Fu, Zheng-Wen, and Yang, Xiao-Qing. High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries. United States: N. p., 2016. Web. doi:10.1002/aenm.201600597.
Zhou, Yong-Ning, Yue, Ji-Li, Hu, Enyuan, Li, Hong, Gu, Lin, Nam, Kyung-Wan, Bak, Seong-Min, Yu, Xiqian, Liu, Jue, Bai, Jianming, Dooryhee, Eric, Fu, Zheng-Wen, & Yang, Xiao-Qing. High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries. United States. doi:10.1002/aenm.201600597.
Zhou, Yong-Ning, Yue, Ji-Li, Hu, Enyuan, Li, Hong, Gu, Lin, Nam, Kyung-Wan, Bak, Seong-Min, Yu, Xiqian, Liu, Jue, Bai, Jianming, Dooryhee, Eric, Fu, Zheng-Wen, and Yang, Xiao-Qing. 2016. "High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries". United States. doi:10.1002/aenm.201600597. https://www.osti.gov/servlets/purl/1336072.
@article{osti_1336072,
title = {High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries},
author = {Zhou, Yong-Ning and Yue, Ji-Li and Hu, Enyuan and Li, Hong and Gu, Lin and Nam, Kyung-Wan and Bak, Seong-Min and Yu, Xiqian and Liu, Jue and Bai, Jianming and Dooryhee, Eric and Fu, Zheng-Wen and Yang, Xiao-Qing},
abstractNote = {Using fast time-resolved in situ X-ray diffraction, charge-rate dependent phase transition processes of layer structured cathode material LiNi1/3Mn1/3Co1/3O2 for lithium-ion batteries are studied. During first charge, intermediate phases emerge at high rates of 10C, 30C, and 60C, but not at low rates of 0.1C and 1C. These intermediate phases can be continuously observed during relaxation after the charging current is switched off. After half-way charging at high rate, sample studied by scanning transmission electron microscopy shows Li-rich and Li-poor phases' coexistence with tetrahedral occupation of Li in Li-poor phase. Also, the high rate induced overpotential is thought to be the driving force for the formation of this intermediate Li-poor phase. The in situ quick X-ray absorption results show that the oxidation of Ni accelerates with increasing charging rate and the Ni4+ state can be reached at the end of charge with 30C rate. Finally, these results give new insights in the understanding of the layered cathodes during high-rate charging.},
doi = {10.1002/aenm.201600597},
journal = {Advanced Energy Materials},
number = 21,
volume = 6,
place = {United States},
year = 2016,
month = 8
}

Journal Article:
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  • For LiMO 2 (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li 2MoO 3). A ‘unit cell breathing’ mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in ‘normal’ materials. The cation mixing caused by migration of molybdenummore » ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.« less
  • Through a systematic study of lithium molybdenum trioxide (Li 2MoO 3), a new ‘unit cell breathing’ mechanism is introduced based on both crystal and electronic structural changes of transition metal oxide cathode materials during charge–discharge: For widely used LiMO 2 (M = Co, Ni, Mn), lattice parameters, a and b, contracts during charge. However, for Li 2MoO 3, such changes are in opposite directions. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of M–M bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking M–O asmore » controlling factor in ‘normal’ materials. The cation mixing caused by migration of Mo ions at higher oxidation state provides the benefits of reducing the c expansion range in early stage of charging and suppressing the structure collapse at high voltage charge. These results open a new strategy for designing and engineering layered cathode materials for high energy density lithium-ion batteries.« less
  • LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less